CN102245668B - Terephthalic acid-based polyester polyols - Google Patents

Terephthalic acid-based polyester polyols Download PDF

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CN102245668B
CN102245668B CN200980150589.0A CN200980150589A CN102245668B CN 102245668 B CN102245668 B CN 102245668B CN 200980150589 A CN200980150589 A CN 200980150589A CN 102245668 B CN102245668 B CN 102245668B
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acid
oil
polyester polyol
glycol
derivative
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CN102245668A (en
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L·葛林格
G·坎普夫
G·蒂舍尔
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4219—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from aromatic dicarboxylic acids and dialcohols in combination with polycarboxylic acids and/or polyhydroxy compounds which are at least trifunctional
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
    • C08G18/4252—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing polyether groups and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4288—Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/127—Acids containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/46—Polyesters chemically modified by esterification
    • C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid

Abstract

Polyester polyol contains the esterification product of a) 10 to 70 mol-% of a dicarboxylic acid composition containing a1) from 50 to 100 mol-% of a terephthalic acid-based material selected from terephthalic acid, dimethyl terephthalate and polyalkylene terephthalate and mixtures thereof, a2) 0 to 50 mol-% of phthalic acid, phthalic acid anhydride or isophthalic acid, a3) 0 to 50 mol-% of one or more dicarboxylic acids, b) 2 to 30 mol-% of one or more fatty acids and/or fatty acid derivatives and/or benzoic acid, c) 10 to 70 mol-% of one or more aliphatic or cycloaliphatic diols with 2 to 18 C atoms or alkoxylates thereof, d) 2 to 50 mol-% of a highly functional polyol selected from the group consisting of glycerin, alkoxylated glycerin, trimethylol propane, alkoxylated trimethylol propane, pentaerythritol and alkoxylated pentaerythritol, wherein at least 200 mmol,; preferably at least 500 mmol and especially preferred at least 800 mmol of polyols d) with an OH functionality of not less than 2.9 are converted per kg of polyester polyol.

Description

Polyester polyol based on terephthalic acid
The present invention relates to polyester polyol based on terephthalic acid and they for the preparation of the purposes of rigid polyurethane foam.
By by the organic diisocyanate of organic or modification or polyisocyanates and the compound with the relative high molecular of at least two reactive behavior hydrogen atoms---particularly with the polyether glycol being obtained by alkylene oxide polymerization or the polyester polyol that obtained by alcohol and dicarboxylic acid polycondensation---at catalysts for polyurethanes, chain extension agent and/or linking agent, under the existence of whipping agent and other auxiliary agents and additive reaction to prepare rigid polyurethane foam be known and be described in a large amount of patents and Literature publication thing in.
Can mention by way of example by Dr.R.Vieweg and Dr.A.
Figure GDA00003205715000011
editor's Kunststoffhandbuch, Volume VII, Polyurethane, Carl-Hanser-Verlag, Munich, 1st Edition1966, and the 2nd Edition1983 being edited by Dr.G.Oertel and 3rd Edition1993.To forming with the suitable selection of component and their ratio, make to generate the polyurethane foam with extraordinary mechanical characteristics.
When using polyester polyol, conventionally adopt dicarboxylic acid aromatics and/or aliphatic and the polycondensation of alkane glycol and/or alkane triol or ether glycol.Yet, also processable polyester waste material, particularly polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) waste material.The method of whole series is known and is described for this purpose.Certain methods is for example, to the conversion of the diester (dimethyl terephthalate (DMT)) of terephthalic acid based on polyester.DE-A1003714 and US-A5,051,528 has described this type of transesterify of using methyl alcohol and transesterification catalyst.
Be known that equally ester based on the terephthalic acid ester aspect combustionproperty than based on phthalic acid is excellent.Yet the high crystallization trend of the ester based on terephthalic acid and the low stability in storage therefore having are shortcomings.
In order to improve the stability in storage of the polyester polyol that is tending towards rapid crystallization based on terephthalic acid, conventionally add aliphatic dicarboxylic acid.Yet this combustionproperty (flame retardant resistance) to the polyurethane foam of preparing thus has disadvantageous effect.
An object of the present invention is to provide based on terephthalic acid or terephthaldehyde acid derivative and there is the polyester polyol of improved stability in storage.Another object of the present invention is to provide the polyester polyol with improved stability in storage, and described polyester polyol provides the polyurethane foam with improved combustionproperty.
The polyester polyol of the product of the esterification of described object by comprising following material is realized:
A) 10mol% to 70mol%, preferably 20mol% to 70mol% and particularly preferably the dicarboxylic acid composition of 25mol% to 50mol%, described dicarboxylic acid composition comprises
A1) material based on terephthalic acid of 50mol% to 100mol%, described material is selected from terephthalic acid, dimethyl terephthalate (DMT), polyalkylene terephthalates (polyalkylene terephthalate) and their mixture;
A2) 0 to 50mol% phthalic acid, Tetra hydro Phthalic anhydride or m-phthalic acid;
A3) one or more dicarboxylic acid of 0 to 50mol%;
B) 2mol% to 30mol%, preferably 3mol% to 20mol%, the particularly preferably lipid acid of 4mol% to 15mol%, one or more derivative of fatty acid and/or phenylformic acid;
C) 10mol% to 70mol%, 20mol% to 60mol% preferably, particularly preferably one or more of 25mol% to 55mol% have aliphatic series or alicyclic diol or their alcoxylates of 2 to 18 carbon atoms;
D) 2mol% to 50mol%, 2mol% to 40mol% preferably, the polyvalent alcohol of the higher functionality of 2mol% to 35mol% particularly preferably, described polyvalent alcohol is selected from glycerine, oxyalkylated glycerine, TriMethylolPropane(TMP), oxyalkylated TriMethylolPropane(TMP), tetramethylolmethane and oxyalkylated tetramethylolmethane;
At least 200mmol of every kg polyester polyol wherein, preferably at least 500mmol and particularly preferably the polyvalent alcohol d of the OH functionality of the having of 800mmol >=2.9 at least) react.
Described dicarboxylic acid composition a) preferably comprises the material a1 based on terephthalic acid that is greater than 50mol%), preferably comprise the material a1 based on terephthalic acid that is greater than 75mol% and particularly preferably comprises 100mol%).
Described aliphatic diol is preferably selected from ethylene glycol, glycol ether, polyoxyethylene glycol, propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 2-methyl isophthalic acid, ammediol, 3-methyl isophthalic acid, 5-pentanediol and their alcoxylates, particularly their ethoxylate.Particularly, described aliphatic diol is glycol ether.
The derivative b of described lipid acid or described lipid acid) preferably based on reproducible raw-material lipid acid or derivative of fatty acid and be selected from Viscotrol C, polyhydrony fatty acid, ricinolic acid, the oil of hydroxyl modification, raisin seed oil, black cumin oil (black cumin oil), pumpkin seed oil (pumpkin kernel oil), Borrago officinalis seed oil (borage seed oil), soybean oil, wheatgerm oil, rapeseed oil, sunflower oil, peanut oil, Prunus amygdalus oil, pistachio oil, almond oil, sweet oil, Queensland nut oil (macadamia nut oil), Lipoval A, arrow-leaved oleaster oil, sesame oil, cannabis oil (hemp oil), hazelnut oil, primrose oil (primula oil), wild rose oil (wild rose oil), Thistle oil, walnut oil, based on Oleomyristic acid, Zoomeric acid, oleic acid, vaccenic acid, petroselinic acid, cis-9-20 carbon acid (gadoleic acid), erucic acid, Selacholeic acid, linolic acid, α-and gamma-linolenic acid, therapic acid (stearidonic acid), arachidonic acid, timnodonic acid, lipid acid and the fatty acid ester of the hydroxyl modification of clupanodonic acid and docosahexenoic acid (cervonic acid).
Under common esterification or transesterification conditions, carry out described esterification or transesterification reaction.In the present invention, at catalyst-free or preferably at catalyst for esterification reaction, advantageously in the atmosphere of rare gas element (such as nitrogen, carbon monoxide, helium, argon etc.), in the melt of the temperature of 150 to 260 ℃ (preferably at 180 to 250 ℃), if under reduced pressure suitable, by described aromatics and aliphatic diacid or dicarboxylic ester and polyol reaction, distill out the low-molecular-weight alcohol (for example methyl alcohol) discharging by transesterification reaction simultaneously, described distillation is preferably under reduced pressure carried out.Possible esterifying catalyst for for example iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin catalyst, described catalyzer be the form of metal, metal oxide or metal-salt.Transesterify also can for example, be carried out under the existence of thinner and/or entrainment agent (benzene,toluene,xylene or chlorobenzene), thereby the water of condensation is distilled as azeotrope.
The present invention also provides by following material being reacted to the method for preparing rigid polyurethane foam:
A) organic diisocyanate of organic and/or modification and/or polyisocyanates and
B) specific polyester polyol of the present invention, described B component) can comprise other polyester polyols that are up to 50 % by weight;
C) if suitable, Aethoxy Sklerol and/or there are at least two to respond other compounds of active group of isocyanate groups, and if suitable, and chain extension agent and/or linking agent;
D) whipping agent;
E) catalyzer and, if suitable,
F) other auxiliary agents and/or additive;
G) fire retardant.
In order to prepare described rigid polyurethane foam by method of the present invention, except above-mentioned specific polyester polyol, also the known formation component of use itself, can provide following detailed description about forming by component.
The organic multiple isocyanate A of possible organic and/or modification) be aliphatic, alicyclic, araliphatic polyisocyanates, and be preferably known aromatics polyfunctional isocyanate itself.
Concrete example is: the two isocyanic acid alkylene esters in alkylidene group with 4 to 12 carbon atoms, for example 1,12-bis-isocyanic acid dodecyl esters, 1,4-bis-isocyanic acid 2-ethyl four methylene esters, 1,5-bis-isocyanic acid 2-methyl five methylene esters, 1,4-tetramethylene diisocyanate, and be preferably 1,6-, bis-isocyanic acid six methylene esters; Alicyclic diisocyanate, for example 1, the any mixture of 3-and Isosorbide-5-Nitrae-bis-NSC 87419 and these isomer, 1-isocyanide acyl group-3,3,5-trimethylammonium-5-isocyanide acyl group methylcyclohexane (IPDI), 2,4-and 2,6-, bis-isocyanic acid hexahydrobenzene methylene esters and corresponding isomer mixture, 4,4'-, 2,2 '-and 2,4 '-bis-isocyanic acid dicyclohexyl methyl esters and corresponding isomer mixture; And be preferably aromatic diisocyanate and polyisocyanates, for example: 2,4-and 2,6-, bis-isocyanic acid benzene methylene esters and corresponding isomer mixture; 4,4'-, 2,4 '-and 2,2 '-bis-isocyanic acid phenylbenzene methyl esters and corresponding isomer mixture; 4,4'-and 2, the mixture of 2 '-bis-isocyanic acid phenylbenzene methyl esters, many methylenes of the many phenyl of polyisocyanic acid ester; 2,4'-, 2,4 '-and the mixture (thick MDI) of 2,2 '-bis-isocyanic acid diphenyl methyl esters and many methylenes of the many phenyl of polyisocyanic acid ester and the mixture of thick MDI and two isocyanic acid benzene methylene esters.Described organic diisocyanate and polyisocyanates can be separately or are used with their form of mixture.
Preferred vulcabond and polyisocyanates are the mixture (MDI of polymerization or PMDI) of two isocyanic acid benzene methylene esters (TDI), two isocyanic acid phenylbenzene methyl esters (MDI) and particularly two isocyanic acid phenylbenzene methyl esters and many methylenes of polyisocyanic acid polyphenylene ester.
Also often use the polyfunctional isocyanate of modification, pass through the product of the chemical reaction acquisition of organic diisocyanate and/or polyisocyanates.Vulcabond and/or the polyisocyanates of the example that can mention for comprising ester group, urea groups, biuret groups, allophanate group, carbodiimide, isocyanurate group, uretdion (uretdione), carbamate groups and/or urethane ester group.
Very particularly preferably use the MDI of polymerization for the preparation of rigid polyurethane foam.
In the prior art, sometimes conventionally isocyanurate group is attached in polyisocyanates.Preferably use the catalyzer (for example using or combine with tertiary amine separately an alkali metal salt of use) that forms isocyanurate group to carry out described combination.The formation of isocyanuric acid ester causes forming fire-retardant polyisocyanurate foam (PIR foam), and described foam is preferably used for industrial rigid foams, for example, as insulcrete or sandwich component, be used for house and buildings.
Other suitable polyester polyols can for example be prepared by organic dicarboxylic acid (being preferably the aliphatic dicarboxylic acid with 4 to 6 carbon atoms) and the polyvalent alcohol (be preferably and have 2 to 12 carbon atoms, preferably have the dibasic alcohol of 2 to 6 carbon atoms) with 2 to 12 carbon atoms.Possible dicarboxylic acid is for example succsinic acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid, decane dicarboxylic acid, toxilic acid, fumaric acid, phthalic acid, m-phthalic acid and terephthalic acid.Described dicarboxylic acid can be used individually or with the form of the mixture with another kind of dicarboxylic acid.Also can use corresponding dicarboxylic acid derivatives, for example, there is dicarboxylic ester or the dicarboxylic anhydride of the alcohol of 1 to 4 carbon atom, thereby replace free dicarboxylic acid.The weight ratio of preferably using succsinic acid, pentanedioic acid and hexanodioic acid is the dicarboxylic acid mixture of for example 20-35:35-50:20-32 and hexanodioic acid particularly preferably.The example of binary and polyvalent alcohol, particularly dibasic alcohol is: ethylene glycol, glycol ether, 1,2-or 1,3-PD, dipropylene glycol, BDO, 1,5-PD, 1,6-hexylene glycol, decamethylene-glycol, glycerine, TriMethylolPropane(TMP) and tetramethylolmethane.Preferably make spent glycol, glycol ether, BDO, 1,5-PD, 1, the mixture of the mixture, particularly BDO of 6-hexylene glycol or at least two kinds of mentioned glycol, 1,5-PD and 1,6-hexylene glycol.Also can use for example, polyester polyol or hydroxycarboxylic acid (for example ω-hydroxycaproic acid) derived from lactone (6-caprolactone).
In order to prepare described polyester polyol, can there is no catalyzer or preferably under esterifying catalyst, advantageously in the atmosphere of rare gas element (such as nitrogen, carbon monoxide, helium, argon etc.), in the melt of the temperature of 150 to 260 ℃ (preferably at 180 to 250 ℃), if under reduced pressure suitable, acid number for example, by described organic (aromatics and preferred aliphatic series) poly carboxylic acid and/or derivative and polyvalent alcohol polycondensation to expectation, described acid number is advantageously less than 10, is preferably less than 2.In a preferred embodiment, esterification mixture, under said temperature, is being less than to 500mbar under barometric point and subsequently, is being preferably polycondensation to 80 under 40 to 200mbar pressure and, to 20, is preferably 40 to 20 acid number.Possible esterifying catalyst for for example iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin catalyst, described catalyzer be the form of metal, metal oxide or metal-salt.For example, yet described polycondensation also can, in liquid phase, be carried out, thereby the water of condensation is distilled as azeotrope under the existence of thinner and/or entrainment agent (benzene,toluene,xylene or chlorobenzene).
In order to prepare described polyester polyol, described organic poly carboxylic acid and/or derivative and polyvalent alcohol are advantageously preferably 1:1.05-1.9 with 1:1-2.1() mol ratio carry out polycondensation.
The polyester polyol obtaining preferably has 2 to 4, and 2 to 3 functionality and 300 to 3000 is particularly preferably 400 to 1000 and the molecular weight of 450-800 particularly.
Also can use the polyether glycol of preparing by known method simultaneously, one or more alkylene oxides for example in alkylidene group with 2 to 4 carbon atoms, for example, by using alkali metal hydroxide (sodium hydroxide or potassium hydroxide), or alkali metal alcoholates (sodium methylate for example, sodium ethylate or potassium ethylate or potassium isopropoxide) as catalyzer, add at least one to comprise 2 to 8 simultaneously, the startup molecule (starter molecule) that is preferably 2 to 6 reactive behavior hydrogen atoms carries out anionoid polymerization to be prepared, or for example, by using Lewis acid (antimony pentachloride, boron fluoride etherate etc.), or Fuller's earth carries out cationoid polymerisation as catalyzer to be prepared.
Suitable oxirane is for example tetrahydrofuran (THF), 1，3-epoxypropane, 1,2-or 2,3-butylene oxide ring, Styrene oxide 98min. and be preferably oxyethane and 1,2 epoxy prapane.Described oxirane can be individually, alternately or as mixture use continuously.Preferred oxirane is propylene oxide and oxyethane, and oxyethane particularly preferably.
Possible startup molecule is for for example: water, organic dicarboxylic acid (succsinic acid for example, hexanodioic acid, phthalic acid and terephthalic acid), aliphatic series with aromatics, unsubstituted or by N-monoalkyl, N, N-dialkyl group and N, the diamines in alkyl with 1 to 4 carbon atom that N '-dialkyl group replaces (quadrol unsubstituted or that replaced by monoalkyl and dialkyl group for example, diethylenetriamine, Triethylenetetramine (TETA), 1, 3-propylene diamine, 1, 3-or 1, 4-butanediamine, 1, 2-, 1, 3-, 1, 4-, 1, 5-and 1, 6-hexamethylene-diamine, phenylenediamine, 2, 3-, 2, 4-and 2, 6-tolylene diamine and 4, 4 '-, 2, 4 '-and 2, 2 '-diaminodiphenyl-methane).
Other possible startup molecules are: alkanolamine (for example thanomin, N-Mono Methyl Ethanol Amine and N-ehtylethanolamine), dioxane hydramine (for example diethanolamine, N methyldiethanol amine and N-ethyldiethanolamine) and three alkanolamines (for example trolamine) and ammonia.Preferably use binary or polyvalent alcohol, ethylene glycol, 1 for example, 2-and 1,3-PD, glycol ether, dipropylene glycol, BDO, 1,6-hexylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, quadrol, sorbyl alcohol and sucrose.
Described polyether glycol, preferably polyoxypropylene and polyoxypropylene-polyoxyethylene polyols have the functionality and 300 to 3000 that is preferably 2 to 6 and particularly 2 to 5, are preferably 300 to 2000 and 400 to 1000 molecular weight particularly.
The polyether glycol that other suitable polyether glycols are polymer modification, be preferably grafted polyether polyol, those of styrene-based and/or vinyl cyanide particularly, it passes through vinyl cyanide, the mixture of vinylbenzene or preferably vinylbenzene and vinyl cyanide is (for example, with 90:10 to 10:90, be preferably the weight ratio of 70:30 to 30:70) advantageously in above-mentioned polyether glycol, use with at German Patent text 1111394, 1222669(US3, 304, 273, 3, 383, 351, 3, 523, 093), 1152536(GB1040452) and 1152537(GB987, 618) those similar methods of describing in are carried out in-situ polymerization and are prepared, and the polyureas that comprises the tertiary amino that for example contains combination, polyhydrazide, urethane and/or trimeric cyanamide (are generally 1 % by weight to 50 % by weight as disperse phase, be preferably the amount of 2 % by weight to 25 % by weight) polyether glycol dispersion, and described dispersion is described in for example EP-B011752(US4,304,708), US-A, 4,374,209 and DE-A, 3231497.
As polyester polyol, described polyether glycol can be used individually or with the form of mixture.Also can be by it with grafted polyether polyol or polyester polyol and mix with the polyesteramide that comprises hydroxyl, polyacetal, polycarbonate and/or polyether polyamine (polyether polyamine).
The compound of the possible polyacetal that comprises hydroxyl for for example can for example, being prepared by glycol (glycol ether, triglycol, 4,4 '-dihydroxyl ethoxy diphenyl base dimethylmethane, hexylene glycol) and formaldehyde.Suitable polyacetal also can be prepared by the polymerization of cyclic acetal.
The possible polycarbonate that comprises hydroxyl is those of itself known type, described polycarbonate can be by for example for example, by glycol (1, ammediol, 1,4-butyleneglycol and/or 1,6-hexylene glycol, glycol ether, triglycol or Tetraglycol 99) for example, prepare with diaryl carbonate (diphenyl carbonate) or phosgene reaction.
Described polyesteramide for example comprises the condenses that is mainly straight chain that the mixture by polynary, saturated and/or undersaturated carboxylic acid or their acid anhydrides and polynary saturated and/or undersaturated amino alcohol or polyvalent alcohol and amino alcohol and/or polyamine obtains.
Suitable polyether polyamine can be prepared by known method by above-mentioned polyether glycol.Can mention by way of example the ω-cyanoalkyl to polyoxy sub alkyl polylol (polyoxyalkylene polyols), then to form hydrogenation (US3267050), or under the existence of hydrogen and catalyzer, use amine or the partially or completely amination (DE1215373) of ammonia to polyoxy sub alkyl polylol.
Described rigid polyurethane foam can be used chain extension agent and/or linking agent C) prepare.Yet, the adding to be proved to be of chain extension agent, linking agent or (if suitable) their mixture be conducive to change mechanical property (for example hardness).As chain extension agent and/or linking agent, use to have to be less than 400, be preferably glycol and/or the triol of 60 to 300 molecular weight.Likely for example have 2 to 14, be preferably the aliphatic series of 4 to 10 carbon atoms, alicyclic and/or araliphatic glycol, ethylene glycol, 1 for example, ammediol, 1,10-decanediol, neighbour,, to dihydroxyl hexanaphthene, glycol ether, dipropylene glycol and be preferably 1,4-butyleneglycol, 1,6-hexylene glycol and two (2-hydroxyethyl) quinhydrones; Triol, for example 1,2,4-, 1,3,5-trihydroxy-hexanaphthene, glycerine and TriMethylolPropane(TMP); Start molecule with low-molecular-weight polyalkylene oxides (polyalkylene oxide) conduct based on oxyethane and/or 1,2 epoxy prapane and above-mentioned glycol and/or triol that comprises hydroxyl.
There are at least two to the isocyanic ester active group that responds, there are at least two to respond other possible Compound C of active hydrogen atom of isocyanic ester) particularly there are those of two or more reaction active groups, described reaction active groups is selected from OH base, SH base, NH base, NH 2base and CH-acidic group, for example beta-diketon base.
If adopt chain extension agent, linking agent or their mixture to be used for generating described rigid polyurethane foam, they are based on B component) weighing scale, advantageously, with 0 to 20 % by weight, preferably with the amount of 0.5 % by weight to 5 % by weight, use.
For generating the whipping agent D of rigid polyurethane foam) preferably include water, formic acid and their mixture.Thereby they form carbonic acid gas and reacts generation carbonic acid gas and carbon monoxide the formic acid in the situation that with isocyanic ester radical reaction.In addition, can use for example lower boiling hydrocarbons of pneumatogen.Suitable pneumatogen has lower than 100 ℃ for the liquid that is inertia to the polyisocyanates of organic, modification or non-modification and its under barometric point, preferably lower than the boiling point of 50 ℃, so that they gasify under the condition of the polymerization addition reaction of heat release.The example of this class I liquid I that can preferably use is alkane (heptane for example, hexane, Skellysolve A and iso-pentane, be preferably the cuts of Skellysolve A and iso-pentane, normal butane and Trimethylmethane and propane), naphthenic hydrocarbon (for example pentamethylene and/or hexanaphthene), ether (furans for example, dme and diethyl ether), ketone (for example acetone and methyl ethyl ketone), alkyl carboxylates (methyl-formiate for example, dimethyl oxalate and ethyl acetate) and halohydrocarbon (methylene dichloride for example, Dichloromonofluoromethane, methylene fluoride, trifluoromethane, C2H4F2 C2H4F2, Tetrafluoroethane, chloro C2H4F2 C2H4F2, 1, 1-bis-chloro-2, 2, 2-Halothane, 2, the chloro-2-fluoroethane of 2-bis-and heptafluoro-propane.Also can use these lower boiling liquid to each other and/or with other the mixture of substituted or unsubstituted hydrocarbon.The organic carboxyl acid for example carboxylic compound of formic acid, acetic acid, oxalic acid, ricinolic acid and bag is also suitable.
Preferably make the mixture of water, formic acid, chloro methylene fluoride, chloro C2H4F2 C2H4F2, dichloro fluoroethane, pentane admixture, hexanaphthene and at least two kinds of described whipping agents, for example the mixture of water and hexanaphthene, chloro methylene fluoride and 1-are chloro-2,2-C2H4F2 C2H4F2 and optionally with the mixture of water.
Described whipping agent completely or partially can be dissolved in polyol component (being B+C+E+F+G) or by static mixer and introduce before polyol component is about to foaming.With regard to water or formic acid, for example conventionally it is dissolved in fully or partly in described polyol component then, by described pneumatogen (pentane) and if suitable, and the residuum of described chemical foaming agent " online " is introduced.
The whipping agent using or the amount of blowing agent blends are 1 % by weight to 45 % by weight, are preferably 1 % by weight to 30 % by weight, and 1.5 % by weight to 20 % by weight particularly preferably, in all cases based on B component) to G) summation meter.
If water is as whipping agent, preferably based on formation B component) meter, the amount by it with 0.2 % by weight to 5 % by weight adds described formation B component).Can be combined adding with the use of whipping agent described in other of water.
Catalyzer E for the preparation of described polyurethane foam) particularly accelerate consumingly B component) comprise reactive behavior hydrogen atom (particularly hydroxyl) if compound and---uses---C) with the polyisocyanates A of organic, modification or non-modification) the compound reacting.
Advantageously use alkaline catalysts for polyurethanes, for example tertiary amine is such as triethylamine, Tributylamine, dimethyl benzylamine, dicyclohexyl methylamine, dimethylcyclohexylamine, two (N, N-dimethyl aminoethyl) ether, two (dimethylaminopropyl) urea, N-methylmorpholine or N-ethylmorpholine, N-cyclohexyl morpholine, N, N, N ', N '-Tetramethyl Ethylene Diamine, N, N, N ', N '-tetramethyl butane diamine, N, N, N ', N '-tetramethyl-oneself-1,6-diamines, five methyl diethylentriamine, lupetazin, N-dimethyl aminoethyl piperidines, 1,2 dimethylimidazole, 1-azabicyclic [2.2.0] octane, Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane (Dabco) and chain triacontanol amine compound (trolamine for example, tri-isopropanolamine, N methyldiethanol amine and N-ethyldiethanolamine, dimethylaminoethanol, 2-(N, N-dimethylamino ethoxy) ethanol, N, N ', N ' '-tri-(dialkyl aminoalkyl) Hexahydrotriazine, N for example, N ', N ' '-tri-(dimethylaminopropyl)-s-Hexahydrotriazine, and triethylenediamine.Yet, metal-salt for example iron protochloride (II), zinc chloride, lead octoate 36 and preferably pink salt for example the mixture of stannous octoate, diethyl caproic acid tin and dibutyl tin dilaurate and particularly tertiary amine and organic tin salt be also suitable.
Other possible catalyzer are: amidine for example 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tetra-alkyl ammonium hydroxide be Tetramethylammonium hydroxide, alkali metal hydroxide for example sodium methylate and potassium isopropoxide and have 10 to 20 carbon atoms of sodium hydroxide and alkali metal alcoholates for example for example, and (if suitable) has an alkali metal salt of the longer chain fatty acid of side chain OH base.0.001 % by weight to 5 % by weight, particularly 0.05 catalyzer of % by weight to 2 % by weight or the combination of catalyzer of weighing scale preferred use based on B component).Also can make reaction carry out the in the situation that of catalyst-free.Under these circumstances, utilize the catalytic activity of the polyvalent alcohol of amine initiation.In the prior art, sometimes conventionally isocyanurate group is attached in polyisocyanates.Described combination is preferably used the catalyzer (for example use separately or with ammonium salt or an alkali metal salt of tertiary amine combination) that forms isocyanurate group to carry out.The formation of isocyanuric acid ester has caused forming fire-retardant PIR foam, and described foam is preferably used for industrial rigid foams, for example, be used as insulcrete or sandwich component for house and buildings.
About above-mentioned and other the further information of raw material, be found in technical literature, Kunststoffhandbuch for example, Volume VII, Polyurethane, Carl Hanser Verlag Munich, Vienna, 1966,1983 and 1993 the 1st, 2 and 3 editions.
If suitable, can add other auxiliary agents and/or additive F to reaction mixture) thus prepare described rigid polyurethane foam.Can mention for surfactant for example, suds-stabilizing agent, hole conditioning agent, filler, dyestuff, pigment, fire retardant, hydrolysis inhibitor, press down mould and antibacterial substance.
Possible surfactant is for for example for helping the homogenizing of raw material and also applicable to the compound of the pore texture of telomerized polymer.Can mention for emulsifying agent for example for example, for example, as the salt of the salt of the sodium salt of the sodium salt of Viscotrol C sulfuric acid or lipid acid and lipid acid and amine (diethylamine oleate, diethanolamine stearate, diethanolamine ricinate), the sulfonic acid (alkali metal salts or ammonium salt of Witco 1298 Soft Acid or dinaphthyl methylene-sulfonic acid and ricinolic acid; Foaming stabiliser is siloxanes-oxyalkylene copolymers and other organopolysiloxane, the alkylphenol of ethoxylation, the fatty alcohol of ethoxylation, paraffin oil, castor-oil plant grease or ricinoleate ester, turkey red oil and peanut oil for example; And hole conditioning agent for example paraffin, fatty alcohol and dimethyl polysiloxane.Above-mentioned have that polyoxy alkylidene and fluoro-alkyl are also applicable to improve emulsifying effect, pore texture as the low-polyacrylate of side group and/or for stable foam.Described surfactant is by B component) weight be 100%, conventionally with the amount of 0.01 % by weight to 10 % by weight, use.
For the purposes of the present invention, filler (particularly reinforcing filler) is common organic and mineral filler, strongthener, weighting agent, for improvement of reagent and the described filler of the polishing machine of paint, coating composition etc., itself is known.Concrete example is: mineral filler is siliceous mineral (for example sheet silicate, as antigorite, serpentine, hornblende, amphibole, chrysotile (chrisotile) and talcum) for example; Metal oxide is kaolin, aluminum oxide, titanium oxide and ferric oxide for example; Metal-salt is chalk, barite for example; With mineral dye such as Cadmium Sulfide and zinc sulphide and glass etc.Preferably use coprecipitate and the natural and synthetic fibrous mineral (for example glass fibre of wollastonite, steel fiber and particularly all lengths) of kaolin (china clay), pure aluminium silicate and barium sulfate and pure aluminium silicate, described fiber can apply with sizing material.Possible organic filler is for example: carbon, trimeric cyanamide, rosin, cyclopentadienyl resins and graftomer and cellulosic fibre, polymeric amide, polyacrylonitrile, urethane, the trevira based on aromatics and/or aliphatic dicarboxylic ester and particularly carbon fiber.
Described inorganic and organic filler can be individually or as mixture use and advantageously by it with based on component A) to C) and weighing scale 0.5 % by weight to 50 % by weight, preferably the amount of 1 % by weight to 40 % by weight adds reaction mixture, and the content of sheet (mat), non-woven fabric and the Woven fabric of natural and synthon can reach the value of 80 % by weight at the most.
As fire retardant G), generally can use the known fire retardant of prior art.Suitable fire retardant is not combinative brominated species, bromination ester, bromination ether (lxol) or bromination alcohol (for example dibromo neopentyl alcohol, tribromoneoamyl alcohol and PHT-4-glycol) and chlorinated phosphate (three (2-chloroethyl) phosphoric acid ester, three (1 for example for example, 3-bis-chloropropyls) phosphoric acid ester, trimethylphenyl phosphoric acid ester, three (2,3-dibromopropyl) phosphoric acid ester, ethylene phosphoric acid four (2-chloroethyl) ester, methane phosphonic acid dimethyl ester, diethanolamino methyl-phosphorous acid diethyl ester and the halogen-containing fire retardant polyvalent alcohol of commercial bag.As other liquid flame retardants, can use phosphoric acid ester or phosphonic acid ester, for example ethyl phosphonic acid diethyl ester (DEEP), triethyl phosphate (TEP), propyl phosphonic acid methyl ester (DMPP), di(2-ethylhexyl)phosphate benzene toluene ester (DPK) and other phosphoric acid ester or phosphonic acid ester.
Except above-mentioned fire retardant, can prepare rigid polyurethane foam fire retardant with following fire retardant: inorganic or organic fire-retardant (for example red phosphorus, the preparation that comprises red phosphorus, hydrated aluminum oxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, arsenic powder, ammonium polyphosphate and calcium sulfate), expansible black lead or cyanogen urea acid derivative (for example trimeric cyanamide), or the mixture of at least two kinds of fire retardants (for example ammonium polyphosphate and trimeric cyanamide) and (if suitable) W-Gum or ammonium polyphosphate, trimeric cyanamide and expansible black lead and/or aromatics or non-aromatic polyester.
Generally speaking, found advantageously to use based on B component) meter, 5 % by weight to 150 % by weight, are preferably the mentioned fire retardant of 10 % by weight to 100 % by weight.
Further information about above-mentioned other common auxiliary agents and additive is found in technical literature, and for example the disquisition of J.H.Saunders and K.C.Frisch " High Polymers " XVI rolls up, Polyurethanes, Parts1 and 2, Interscience Publishers1962 and 1964, or Kunststoff-Handbuch, Polyurethane, VII volume, Hanser-Verlag, Munich, Vienna, the the 1st and the 2nd edition, 1966 and nineteen eighty-three.
In order to generate rigid polyurethane foam of the present invention, by the organic multiple isocyanate A of organic and/or modification), specific polyester polyol B) and (if suitable) polyether glycol and/or there are at least two to isocyanic ester respond other compounds and (if suitable) chain extension agent and/or the linking agent C of active group) react, consumption in described reaction is polyisocyanates A) NCO base and B component) and (if you are using) C) and D) to G) the equivalence ratio of summation of reactive behavior hydrogen atom be 1-6:1, be preferably 1.1-5:1 and particularly 1.2-3.5:1.
Described rigid polyurethane foam is advantageously used a step (one-shot) method to prepare, for example, use high pressure or low-voltage technology, for example, in mould (metal die) open or sealing, carries out.It is also usual that thereby reaction mixture continuous administration to suitable travelling belt is prepared to sheet material.
By starting ingredient at 15 to 90 ℃, be preferably 20 to 60 ℃ and particularly at the temperature of 20 to 35 ℃, mix, then be introduced into open mould, or (if suitable) is under high pressure introduced into the mould of sealing, or the in the situation that of non-stop run station, be administered to and held being with of reaction mixture.As noted above, can use the method for agitator or agitating screw mechanically to mix.Die temperature is advantageously 20 to 110 ℃, is preferably 30 to 70 ℃ and particularly 40 to 60 ℃.
The rigid polyurethane foam generating by method of the present invention has 15 to 300g/l, is preferably 20 to 100g/l and 25 to 60g/l density particularly.
The present invention will be described to use the following example.
Embodiment
Prepared various polyester polyols:
General method
The polyvalent alcohol of dicarboxylic acid, aliphatic series or alicyclic diol or their alcoxylates and higher functionality is incorporated in the round-bottomed flask that is equipped with mechanical stirrer, thermometer and distillation column and nitrogen inlet pipe of 4 liters.After the four butanols titaniums of 40ppm add as catalyzer, this mixture is stirred and be heated to 240 ℃, distill out continuously discharged water simultaneously.This reaction is carried out under 200mbar.The polyesterols of the acid number of had≤1mg of this reaction KOH/g.
Comparing embodiment 1
Use described general method that 894.8g Tetra hydro Phthalic anhydride, 597.35g oleic acid, 865.51g glycol ether and 289.31g glycerine are reacted.Obtain having the polyesterols of the hydroxyl value of 2.2 OH functionality and 259mg KOH/g.
Comparing embodiment 2
Use described general method that 953.58g Tetra hydro Phthalic anhydride, 545.65g oleic acid, 884.79g glycol ether and 266.81g glycerine are reacted.Obtain having the polyesterols of the hydroxyl value of 2.2 OH functionality and 237mg KOH/g.
Comparing embodiment 3
Use the commercially available Invista of deriving from based on dimethyl terephthalate (DMT) and there is the polyesterols (Terate7541LO) of the hydroxyl value of 192mg KOH/g.
Comparing embodiment 4
Use described general method that 1428.51g terephthalic acid, 121.46g oleic acid, 1460g glycol ether and 57.69g TriMethylolPropane(TMP) are reacted.Obtain having the polyesterols of the hydroxyl value of 2.0 OH functionality and 228mg KOH/g.
Comparing embodiment 5
According to described general method, 1468.53g terephthalic acid, 62.43g oleic acid, 1500.9g glycol ether and 40.7g glycerine are reacted.Obtain having the polyesterols of the hydroxyl value of 2.05 OH functionality and 238mg KOH/g.
Embodiment 1
According to described general method, 1188.95g terephthalic acid, 404.36g oleic acid, 1006.3g glycol ether and 384.12g TriMethylolPropane(TMP) are reacted.Obtain having the polyesterols of the hydroxyl value of 2.3 OH functionality and 246mg KOH/g.
Embodiment 2
According to described general method, 1307.33g terephthalic acid, 444.57g oleic acid, 897.73g glycol ether and 362.34g glycerine are reacted.The method obtains having the polyesterols of the hydroxyl value of 2.5 OH functionality and 239mg KOH/g.
The measurement result of stability in storage is summarized in table 1.
Table 1:
Figure GDA00003205715000141
Table 1 demonstrate the polyesterols prepared by method of the present invention can storage-stable over 3 months.
Comparing embodiment 6 and 7 and embodiment 3 and 4
The preparation of rigid polyurethane foam (modification 1):
By isocyanic ester with to isocyanic ester respond active component and whipping agent, catalyzer and every other additive, foam together with the constant ratio of mixture that the polyol component of take is 100:190 with isocyanate component.In all cases, arrange the fiber time (fiber time) constant for 49+/-1 second and total foam density be 33+/-0.5g/l.
Polyol component:
The embodiment 1 of 79 weight parts and 2 or the polyesterols of comparing embodiment 1 and 2
The Aethoxy Sklerol of 6 weight parts, described Aethoxy Sklerol comprises ethylene glycol and has 2 hydroxy functionality and the ether of the oxyethane of the hydroxyl value of 200mg KOH/g
The fire retardant tricresyl phosphate chloro isopropyl ester (TCPP) of 13 weight parts
The stablizer that the stabilizer T egostab B8443(of 2 weight parts comprises siloxanes)
The pentane S80:20 of 15 weight parts
The water of 1.5 weight parts
The potassium acetate of 1.6 weight parts (concentration of 47 % by weight in ethylene glycol)
70% pair of (2-dimethyl aminoethyl) ether of 1.2 weight parts
Isocyanate component:
The polymeric MDI of 190 weight parts (derives from BASF SE, Ludwigshafen, DE's
Figure GDA00003205715000151
m50)
By the content of water, realize foam density and be set to 33+/-1g/l, and by fiber set of time, be 49+/-1s by changing the content of two (2-dimethyl aminoethyl) ethers.
Described component as described in foam mutually.As described below, by indentation test, measure gained rigid polyurethane foam degree of cure and by measuring the height of flame, measure flame retardant resistance.
Measure degree of cure
By indentation test, measure degree of cure., in polystyrene cup, mix after described component 2.5,3,4,5,6 and 7 minutes for this reason, use universal testing machine the steel pressure head with the semi-spherical shape end of 10mm radius to be pressed into the degree of depth of 10mm in foam.For this reason requiredly take peak power the measuring as foam curing degree that N represents.As measuring of the brittleness of rigid polyurethane foam, measured the time point that in the indentation test surface of rigid foams has the visible region of fracture.
Measure flame retardant resistance:
According to EN ISO11925-2, measure the height of flame.This results are shown in table 2.
Table 2
? Comparing embodiment 6 Comparing embodiment 7 Embodiment 3 Embodiment 4
Polyester polyol, from: Comparing embodiment 1 Comparing embodiment 2 Embodiment 1 Embodiment 2
Indentation test after 3 minutes [N] 39 38 50 53
Indentation test after 5 minutes [N] 70 71 84 87
Flame height [cm] 16 18 11 10
As can be seen from Table 2, the rigid polyurethane foam generating by method of the present invention demonstrates improved curing performance and improved combustionproperty.
Comparing embodiment 8 and embodiment 5 and 6
The generation of rigid polyurethane foam (modification 2):
By isocyanic ester with to isocyanic ester respond active component and whipping agent, catalyzer and every other additive, foam together with the constant ratio of mixture that the polyol component of take is 100:190 with isocyanate component.In all cases, arrange the fiber time constant for 49+/-1 second and total foam density be 41+/-1g/l.
Polyol component:
The embodiment 1 of 41.5 weight parts and 2 or the polyesterols of comparing embodiment 2
The OHN with about 490mg KOH/g of 20 weight parts passes through propylene oxide to the Aethoxy Sklerol of preparing as the addition polymerization that starts the sucrose/glycerol mixture of molecule
The OHN with about 160mg KOH/g of 6 weight parts passes through propylene oxide to the Aethoxy Sklerol of preparing as the addition polymerization of TriMethylolPropane(TMP)
The Aethoxy Sklerol of 5 weight parts, described Aethoxy Sklerol comprises ethylene glycol and has 2 hydroxy functionality and the ether of the oxyethane of the hydroxyl value of 200mg KOH/g
The fire retardant tricresyl phosphate chloro isopropyl ester (TCPP) of 25 weight parts
The stablizer that the stablizer Niax Silicone L6635(of 2.5 weight parts comprises siloxanes)
The pentane S80:20 of 7.5 weight parts
The water of 2.0 weight parts
The potassium acetate of 1.5 weight parts (concentration of 47 % by weight in ethylene glycol)
The mixture of two (2-dimethyl aminoethyl) ether of 0.6 weight part and the 1:1 of 4-methyl hexamethylene diamine
Isocyanate component:
The polymeric MDI of 190 weight parts (derives from BASF SE, Ludwigshafen, DE's
Figure GDA00003205715000161
m50)
By the content of pentane, realize foam density and be set to 41+/-1g/l, and by fiber set of time, be 49+/-1s by changing the ratio of mixture of the 1:1 of two (2-dimethyl aminoethyl) ether and 4-methyl hexamethylene diamine.
Component A and B as described in foam mutually.The results are shown in table 3 of indentation test and flame height.
Table 3
? Comparing embodiment 8 Embodiment 5 Embodiment 6
Polyester polyol, from: Comparing embodiment 2 Embodiment 1 Embodiment 2
Indentation test after 3 minutes [N] 53 61 63
Indentation test after 5 minutes [N] 92 101 103
Flame height [cm] 11 7 10
As can be seen from Table 3, the rigid polyurethane foam generating by method of the present invention has demonstrated improved curing performance and improved combustionproperty.
Comparing embodiment 9 and embodiment 7
In addition, by biobelt method, prepared sandwich component.By improving the content to 2.6 part of water rather than 2 parts, and be set to 30+/-1g/l by 11 parts of pentanes rather than 7.5 parts of foam densities.In addition by changing the ratio of mixture of the 1:1 of two (2-dimethyl aminoethyl) ether and 4-methyl hexamethylene diamine, by fiber set of time, be 49+/-1s.
With the comparison ester of the dimethyl terephthalate (DMT) of embodiment 3 and the ester of embodiment 1 carry out described biobelt experiment based on the comparison.The evaluation of definite effects on surface as described below and processibility.
Determining of surface imperfection:
By biobelt method, produce the test sample for the occurrence number of evaluation table plane defect.
Use aforesaid method to measure surface imperfection.For this reason, the foam sample of pre-treatment 20cm x30cm and being illuminated is then taken pictures as mentioned above.Then by the image digitazation of this foam overlapping.Thereby the integral area of the black region of digital picture is obtained to the observed value of the occurrence number of surface imperfection divided by the total area of image.
In addition, the surface properties of rigidity polyisocyanurate foam has been carried out to other qualitative evaluation, wherein removed 1m x2m foam sample top layer then effects on surface carried out the visual evaluation about surface imperfection.
The mensuration of processibility:
By check the formation of foam between processing period, measure processibility.If formed in the skin breakage of foam and also therefore torn the air pocket of the whipping agent of this opening, be marked as " breaking " and cannot process this system in no problem mode.If do not observe this unsafty phenomenon, processing is no problem.
This results are summarized in table 4.
Table 4
? Comparing embodiment 9 Embodiment 7
Polyester polyol, from: Comparing embodiment 3 Embodiment 1
Bottom defect [%]/visual evaluation 16.8%/poor 4.8%/good
Processing Break No problem
Table 4 demonstrate the rigid polyurethane foam generating by method of the present invention can be more easily no problem prepare.
Comparing embodiment 10 and 11 and embodiment 8
Embodiment
The preparation of rigid polyurethane foam (modification 3)
In addition,, according to the preparation of following rigid polyurethane foam, by biobelt method, prepare test sheet (modification 3).
By isocyanic ester with to isocyanic ester respond active component and whipping agent, catalyzer and every other additive, foam together with the constant ratio of mixture that the polyol component of take is 100:170 with isocyanate component.In all cases, arrange the fiber time constant for 28+/-1 second and total foam density be 37+/-1g/l.
Polyol component:
Embodiment's or comparing embodiment 2 the polyesterols of 58 weight parts
The Aethoxy Sklerol of 10 weight parts, described Aethoxy Sklerol comprises ethylene glycol and has 2 hydroxy functionality and the ether of the oxyethane of the hydroxyl value of 200mg KOH/g
The fire retardant tricresyl phosphate chloro isopropyl ester (TCPP) of 30 weight parts
The stablizer that the stabilizer T egostab B(of 2 weight parts comprises siloxanes)
The Skellysolve A of 10 weight parts
The formic acid of 1.6 weight parts (85%)
The potassium formiate of 2.0 weight parts (being the intensity of 36 % by weight in ethylene glycol)
Two (2-dimethyl aminoethyl) ethers (70 % by weight in dipropylene glycol) of 0.6 weight part
Isocyanate component:
The polymeric MDI of 170 weight parts (
Figure GDA00003205715000191
m50)
Change by pentane content realizes foam density and is set to 37+/-1g/l, and by fiber set of time, is 28+/-1s by changing the content of two (2-dimethyl aminoethyl) ethers.
Component A and B as described in foam mutually.The results are summarized in table 5 of surface evaluation and processibility.
Table 5
? Comparing embodiment 10 Comparing embodiment 11 Embodiment 8
Polyester polyol, from: Comparing embodiment 1 Comparing embodiment 2 Embodiment 1
Bottom defect [%]/visual evaluation 24.2%/poor 18.4%/poor 3.6%/good
Processing Break Break No problem
Table 5 demonstrate the rigidity polyisocyanurate foam generating by method of the present invention can be more easily no problem generate.

Claims (11)

1. a polyester polyol, the product that described polyester polyol comprises following material esterification:
A) the dicarboxylic acid composition of 10mol% to 70mol%, described dicarboxylic acid composition comprises
A1) material based on terephthalic acid of 100mol%, described material is selected from terephthalic acid, dimethyl terephthalate (DMT), polyalkylene terephthalates and their mixture;
B) one or more lipid acid and/or the derivative of fatty acid of 2mol% to 30mol%;
C) one or more of 10mol% to 70mol% have aliphatic series or alicyclic diol or their alcoxylates of 2 to 18 carbon atoms;
D) polyvalent alcohol of the higher functionality of 2mol% to 50mol%, described polyvalent alcohol is selected from glycerine, oxyalkylated glycerine, TriMethylolPropane(TMP), oxyalkylated TriMethylolPropane(TMP), tetramethylolmethane and oxyalkylated tetramethylolmethane;
Wherein at least 800mmol's of every kg polyester polyol has >=the polyvalent alcohol d of 2.9 OH functionality) react.
2. the polyester polyol of claim 1, wherein said dicarboxylic acid composition a) comprises the material a1 based on terephthalic acid that is greater than 75mol%).
3. claim 1 or 2 polyester polyol, wherein said aliphatic series or alicyclic diol c) be selected from ethylene glycol, glycol ether, propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 2-methyl isophthalic acid, ammediol and 3-methyl isophthalic acid, 5-pentanediol and their alcoxylates.
4. the polyester polyol of claim 3, wherein said aliphatic diol is glycol ether.
5. claim 1 or 2 polyester polyol, wherein said lipid acid or derivative of fatty acid b) for based on reproducible raw-material lipid acid or derivative of fatty acid and be selected from Viscotrol C, ricinolic acid, the oil of hydroxyl modification, raisin seed oil, black cumin oil, pumpkin seed oil, Borrago officinalis seed oil, soybean oil, wheatgerm oil, rapeseed oil, sunflower oil, peanut oil, Prunus amygdalus oil, pistachio oil, almond oil, sweet oil, Queensland nut oil, Lipoval A, arrow-leaved oleaster oil, sesame oil, cannabis oil, hazelnut oil, primrose oil, wild rose oil, Thistle oil, walnut oil.
6. claim 1 or 2 polyester polyol, wherein said lipid acid or derivative of fatty acid b) for based on reproducible raw-material lipid acid or derivative of fatty acid and be selected from polyhydrony fatty acid.
7. claim 1 or 2 polyester polyol, wherein said lipid acid or derivative of fatty acid b) for based on reproducible raw-material lipid acid or derivative of fatty acid and be selected from based on Oleomyristic acid, Zoomeric acid, oleic acid, vaccenic acid, petroselinic acid, cis-9-20 carbon acid, erucic acid, Selacholeic acid, linolic acid, α-and lipid acid and the fatty acid ester of the hydroxyl modification of gamma-linolenic acid, therapic acid, arachidonic acid, timnodonic acid, clupanodonic acid and docosahexenoic acid.
8. generate a method for rigid polyurethane foam, described method is by carrying out following substance reaction:
A) organic multiple isocyanate of organic and/or modification with
B) polyester polyol of definition in claim 1, described B component) can comprise other polyester polyols that are up to 50 % by weight;
C) if suitable, if Aethoxy Sklerol and/or there are at least two to isocyanic ester respond other compounds and---suitable---and chain extension agent and/or the linking agent of active group;
D) whipping agent;
E) catalyzer and, if suitable,
F) other auxiliary agents and/or additive;
G) fire retardant.
9. the method for claim 8, wherein said polyisocyanates comprises vulcabond.
10. the rigid polyurethane foam that can obtain by the method for claim 8 or 9.
The polyester polyol of 11. claims 1 is for generating the purposes of rigid polyurethane foam.
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